High Performance, Low Toxicity Hypergolic Fuel

ABSTRACT

Disclosed is a group of tertiary amine azides useful as hypergolic fuels for hypergolic bipropellant mixtures. The fuels provide higher density impulses than monomethyl hydrazine (MMH) but are less toxic and have lower vapor pressures that MMH. In addition, the fuels have shorter ignition delay times than dimethylaminoethylazide (DMAZ) and other potential reduced toxicity replacements for MMH.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The U.S. Government may have certain rights in this invention pursuant to Contract No. W31PQ06C0167 awarded by the U.S. Army

CROSS-REFERENCE TO RELATED APPLICATIONS

Not Applicable

INCORPORATED-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC

Not Applicable

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a hypergolic rocket fuels that simultaneously possess high-performance propellant characteristics and low toxicity relative to Monomethylhydrazine (MMH). The fuels provide propellant performance as high as or higher than MMH, but have lower toxicity.

2. Description of Related Art

Monomethylhydrazine (MMH) is a widely employed fuel in hypergolic, bipropellant systems. MMH possesses desirable propellant properties but it is highly toxic, carcinogenic, and corrosive. Although gelling has dramatically improved the safety of handling and storing the propellant, its toxicity and carcinogenicity are still of major concern. Therefore, there is a need for alternative liquid hypergolic fuels that are less carcinogenic and less toxic than MMH but also have equal or higher energy densities, lower vapor pressures and ignition delays than MMH. These fuels, like MMH, may be used in the form of gels to further improve safety.

Although DMAZ is hypergolic, its ignition delay with IRFNA is significantly longer than MMH. A longer ignition delay requires a larger combustion chamber to avoid pressure spikes that can damage the engine.

U.S. Pat. No. 6,013,143, incorporated by reference herein in its entirety, discloses three chemicals, each comprising a tertiary nitrogen and an azide functional group that are hypergolic when mixed with an oxidizer such as IRFNA, hydrogen peroxide, nitrogen tetroxide, and hydroxyl ammonium nitrate. The chemicals are dimethylaminoethylazide (DMAZ), pyrollidineylethylazide (PYAZ), and bis (ethyl azide)methylamine (BAZ). Inhibited Red Fuming Nitric Acid (IRFNA) type IIIB and monomethyl hydrazine (MMH) deliver a specific impulse of 284 Ib_(f) sec/Ib_(m) and a density impulse of 13.36 Ib_(f) sec/cubic inch in a rocket engine operating a pressure of 2000 psi. DMAZ, PYAZ, and BAZ are proposed as potential replacements for MMH. DMAZ, under the same conditions as MMH, delivers a specific impulse of 287 Ib_(f) sec/Ib_(m) and a density impulse of 13.8 Ib_(f) sec/cubic inch. The patent discloses the mixing of the hypergolic fuel chemicals with gellants and additives such as aluminum and boron to increase specific impulse and density impulse values.

U.S. Pat. No. 6,926,633, incorporated by reference herein in its entirety, discloses a family of amine azides having cyclic structures and for use as hypergolic rocket propellants. The amine azide compounds comprise at least one amine, including tertiary amines, and an azide functional group pendant from a cyclic structure. The propellants are disclosed as being used with oxidizers and, optionally with catalysts present in fuel or oxidizer. Fuel properties for the amine azides are provided based on computational quantum chemistry calculations.

U.S. Pat. No. 6,949,152, incorporated by reference herein in its entirety, discloses hypergolic propulsion systems comprising a fuel composition and an oxidizer composition. The fuel composition contains an azide compound having at least one tertiary nitrogen and at least one azide functional group. The oxidizer contains hydrogen peroxide in water. The hypergolic reaction between oxidizer and fuel is catalyzed by a transition metal, preferably compounds of cobalt and manganese.

Unlike hypergolic fuels disclosed previously, the present fuels exhibit lower toxicity and higher performance than MMH. The fuels require no catalyst to achieve high performance and are hypergolic with commonly used oxidizers. The fuels of the present invention may be used alone, in combination with each other, or in combination with other fuels in blends.

BRIEF SUMMARY OF THE INVENTION

The present invention is a group of tertiary amine azide chemicals useful as hypergolic fuels for hypergolic bipropellant mixtures. The fuels provide higher density impulses than MMH but are less toxic and have lower vapor pressures that MMH. In addition, the fuels have shorter ignition delay times than DMAZ and other potential reduced toxicity replacements for MMH.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 illustrates the structures of chemicals (I)-(VIII).

FIG. 2 illustrates the structures of chemicals (IX)-(XI).

FIG. 3 illustrates the structures of chemicals (XII) and (XIII).

DETAILED DESCRIPTION OF THE INVENTION

The present invention is a rocket fuel composition comprising one or more of the molecules shown in FIGS. 1-3. The fuel is hypergolic when combined with a strong oxidizer such as IRFNA, hydrogen peroxide, nitrogen tetroxide, or hydroxyl ammonium nitrate. Relevant chemical and physical properties of the molecules have been calculated using validated molecular modeling techniques, including quantum chemistry and Conductor-like Screening MOdel for Real Solvent (COSMO-RS) methods. The fuel molecules have been selected for one or more desirable propellant properties including:

-   -   High heat of formation: Heat of formation is directly related to         the specific impulse which is a measure of energy content in the         molecule.     -   Density: Density of the liquid fuel is important because density         impulse, a measure of fuel performance, is the product of         density and specific impulse.     -   Vapor Pressure: Low vapor pressure improves safety during         handling and storage.     -   Absence of N—N single bonds: Absence of N—N single bonds reduces         toxicity.     -   Short Ignition Delay: Short ignition delay time with the         oxidizer is desirable to minimize engine size and damage         resulting from pressure spikes during combustion.

Heats of Formation

First-principle ab initio quantum chemistry methods are the most accurate and suitable technique for calculations of molecular geometries, heats of formations, and activation barriers. Quantum chemistry techniques are based on the principles of quantum mechanics. The procedure numerically solves a many-electron Schrödinger equation to obtain a molecular wave function and energy. The molecular energies can be used to calculate heats of formation.

CBS-QB3 [Ochterski, 1995; Montgomery, 2000] and PBEPBE/6-311++G(d,p) [Perdew, 1996] combined with isodesmonic reaction methods were used to calculate the heats of formations, and activation barriers for the molecules in FIGS. 1-3. Heat of vaporization was calculated using a COSMO-RS technique [Klamt, 1995 and 2000]. Table 1 shows the computed heats of formation for hydrazine, MMH, DMAZ, and the compounds of the present invention Numbers in parentheses are National Institutes of Standards and Technology (NIST) experimental data. The molecules of the present invention possess higher heats of formation than MMH, and are therefore expected to possess specific impulse values that exceed those for MMH.

Densities

Wong et al. [Wong, 1995] have developed a procedure for calculating molecular volume, defined as the volume occupied by 0.001 au (1 au=6.748 e/Angstrom) electron density envelope. Once the molecular volume is known, the density can be computed using molecular weight. Calculated and known densities were compared for a number of amines and amine azides to validate density calculations.

Calculations were performed at the PBEPBE/6-311++G(d,p) level. Table 2 compares experimentally measured densities with calculated densities with and without corrective correlation. Error! Reference source not found, tabulates the predicted densities of molecules shown in FIGS. 1-3.

TABLE 1 Computed Heats of Formation Gas Phase Gas Phase Molecule ΔH_(f) ^(298 K) kcal/mol ΔH_(f) ^(298 K) cal/gm Hydrazine 23.8 (22.8) 744.9 (712.5) MMH 23.0 (22.6) 500.9 (492.2) DMAZ 73.4 643.6 I 96.2 858.9 II 149.8 1361.9 III 110.1 781.0 IV 134.8 1078.2 V 112.2 738.3 VI 90.0 489.0 VII 112.2 679.7 VIII 110.0 516.3 IX 114.3 747.2 X 89.6 577.8 XI 128.5 537.6 XII 106.5 578.9 XIII 144.6 510.9

TABLE 2 Calculated and Measured Densities Computed Density Experimental Density after Molecule (raw data) density correlation (CH₃)₂NH 0.9307 0.671 0.7038 CH₃NH₂ 0.9140 0.694 0.6849 CH₃N₃ 1.1225 0.869 0.9212 C₂H₅N₃ 1.1187 0.876 0.9170 2-azido-N- 1.1649 0.990 0.9693 cyclopropylethanamine H₂NCH₂CH₂N₃ 1.1791 1.040 0.9855 I, DMAZ 1.1100 0.933 0.9096 HN₃ 1.3116 1.090 1.1356

TABLE 3 Predicted Densities Molecule Density (raw data) Density after using the correlation I 1.1320 0.9346 II 1.1334 0.9362 III 1.2114 1.0246 IV 1.3325 1.1619 V 1.4048 1.2438 VI 1.2153 1.0290 VII 1.3801 1.2158 VIII 1.2347 1.0510 IX 1.2449 1.0626 X 1.1381 0.9415 XI 1.3249 1.1532 XII 1.2433 1.0608 XIII 1.2539 1.0728

Specific and density impulse are the two most important parameters describing the performance of a fuel. Density impulse is a measure of the performance per volume of the fuel. Table 4 shows the computed specific and density impulse for each of the molecules shown in FIGS. 1-3 with IRFNA as the oxidizer.

TABLE 4 Computed Specific and Density Impulse Density % Impulse = density*I_(sp)*10⁻³ Improvement Molecule I_(sp) (lb_(f)-sec/lb_(m)) (lb_(f)-sec/ft³) over MMH I 280.0 16.3 4.1 II 286.4 16.7 6.6 III 280.2 17.9 14.2 IV 280.7 20.4 29.7 V 272.4 21.2 34.7 VI 276.8 17.8 13.3 VII 267.8 20.3 29.5 VIII 278.0 18.2 16.2 IX 283.4 18.8 19.7 X 277.5 16.3 3.9 XI 277.6 20.0 27.3 XII 279.0 18.5 17.7 XIII 278.4 18.6 18.8

The Isp values were calculated using the PROPER thermochemical code and correspond to the optimum fuel/IRFNA ratio. Table 4 shows that there is a substantial improvement of density impulse over MMH.

Synthesis of Hypergolic Fuels

The molecules of the present invention may be synthesized by those skilled in the art using known chemical synthetic reactions. For example, the synthesis of compound V can be accomplished by the using the known condensation of guanidines with haloacetates [Webb, 2003] followed by reaction with PCl₅ and treatment with NaN₃. Compound VII can be prepared from 2,4-dichlorotriazine by sequential substitution of the chlorine atoms. The dichloride 5 can be prepared by condensation [Harris, 1981] of iminyl chloride. The preparation of compound XII can be accomplished, for example, by transamination [Flores-Parra, 1999] between two symmetric triazinanes.

REFERENCES

The following references are incorporated by reference in their entirety.

-   Flores-Parra, A.; Sanchez-Ruiz, S. A. Heterocycles (1999) 51:     2079-2092. -   Godbout, N, Salahub, D. R., Andzelm, J., and Wimmer, E.; Can. J.     Chem. (1992) 70: 560 -   Harris, R. L. N. “The synthesis of Triazines from     N-Cyanocarbamimidates” Synthesis (1981) 1981:907-908 -   Klamt, A; J. Phys. Chem., (1995) 99: 222 -   Klamt A.; Fluid Phase Equil., (2000) 172: 43 -   McQuaid, M. J.; Stevenson, W. H., and Thompson; D. M. (2004) 24th     Army Science Conference, Orlando, Fla. -   Montgomery Jr. J. A., Frisch, M. J. Ochterski, J. W., and     Petersson, G. A. (2000) J. Chem. Phys. 112: 6532. -   Ochterski, J. W., Petersson, G. A., and Wiberg, K. B. (1995) J. Am.     Chem. Soc. 117: 11299 -   Perdew, J. P., Burke, K., and Ernzerhof, M. (1996) Phys. Rev. Lett.     77, 3865 -   Wong, M. W., Wiberg, K. B., Frisch, M. J. (1995) J. Camp. Chem.     16:385 

1. A hypergolic bipropellant combination comprising an oxidizer and a fuel, the fuel comprising an amine azide chemical having the structure (CH₃)₂N—R¹, wherein R¹ is selected from the group consisting of —CHCHN₃, —CCN₃,


2. The hypergolic bipropellant combination of claim 1 further comprising a gellant mixed with the fuel or oxidizer.
 3. The hypergolic bipropellant combination of claim 1 wherein the oxidizer is selected from IRFNA, hydrogen peroxide, nitrogen tetroxide, and hydroxyl ammonium nitrate.
 4. The hypergolic bipropellant combination of claim 1 wherein the fuel is a mixture comprising the amino azide chemical is an additive.
 5. A hypergolic bipropellant combination comprising an oxidizer and a fuel, the fuel comprising an amine azide chemical having the structure:

wherein X is H or CH₃ and R² is selected from the group consisting of: CH₃, CH₂N₃, CHCHN₃, and


6. The hypergolic bipropellant combination of claim 5 further comprising a gellant mixed with the fuel or oxidizer.
 7. The hypergolic bipropellant combination of claim 5 wherein the oxidizer is selected from IRFNA, hydrogen peroxide, nitrogen tetroxide, and hydroxyl ammonium nitrate.
 8. The hypergolic bipropellant combination of claim 5 wherein the fuel is a mixture comprising the amine azide chemical is an additive.
 9. A hypergolic bipropellant combination comprising an oxidizer and a fuel, the fuel comprising an amine azide chemical having the structure:


10. The hypergolic bipropellant combination of claim 9 further comprising a gellant mixed with the fuel or oxidizer.
 11. The hypergolic bipropellant combination of claim 9 wherein the oxidizer is selected from IRFNA, hydrogen peroxide, nitrogen tetroxide, and hydroxyl ammonium nitrate.
 12. The hypergolic bipropellant combination of claim 9 wherein the fuel is a mixture comprising the amine azide chemical is an additive. 